CN112703189B - Novel compound and organic light emitting device comprising the same - Google Patents

Novel compound and organic light emitting device comprising the same Download PDF

Info

Publication number
CN112703189B
CN112703189B CN201980059738.6A CN201980059738A CN112703189B CN 112703189 B CN112703189 B CN 112703189B CN 201980059738 A CN201980059738 A CN 201980059738A CN 112703189 B CN112703189 B CN 112703189B
Authority
CN
China
Prior art keywords
added
mmol
compound
layer
stirred
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201980059738.6A
Other languages
Chinese (zh)
Other versions
CN112703189A (en
Inventor
郑珉祐
李东勋
张焚在
洪玩杓
徐尚德
李征夏
韩修进
朴瑟灿
黄晟现
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
LG Chem Ltd
Original Assignee
LG Chem Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by LG Chem Ltd filed Critical LG Chem Ltd
Priority claimed from PCT/KR2019/016488 external-priority patent/WO2020111780A1/en
Publication of CN112703189A publication Critical patent/CN112703189A/en
Application granted granted Critical
Publication of CN112703189B publication Critical patent/CN112703189B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
    • C07D487/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/14—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D407/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00
    • C07D407/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/12—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains three hetero rings
    • C07D487/14—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D491/00—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00
    • C07D491/02—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00 in which the condensed system contains two hetero rings
    • C07D491/04—Ortho-condensed systems
    • C07D491/044—Ortho-condensed systems with only one oxygen atom as ring hetero atom in the oxygen-containing ring
    • C07D491/048—Ortho-condensed systems with only one oxygen atom as ring hetero atom in the oxygen-containing ring the oxygen-containing ring being five-membered
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
    • C07D493/22—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains four or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
    • C07D495/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
    • C07D495/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
    • C07D495/22—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains four or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D498/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D498/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
    • C07D498/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D513/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00
    • C07D513/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00 in which the condensed system contains two hetero rings
    • C07D513/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D519/00—Heterocyclic compounds containing more than one system of two or more relevant hetero rings condensed among themselves or condensed with a common carbocyclic ring system not provided for in groups C07D453/00 or C07D455/00
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H10K85/622—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing four rings, e.g. pyrene
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H10K85/626—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing more than one polycyclic condensed aromatic rings, e.g. bis-anthracene
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/654—Aromatic compounds comprising a hetero atom comprising only nitrogen as heteroatom
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/656—Aromatic compounds comprising a hetero atom comprising two or more different heteroatoms per ring
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6574—Polycyclic condensed heteroaromatic hydrocarbons comprising only oxygen in the heteroaromatic polycondensed ring system, e.g. cumarine dyes
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6576—Polycyclic condensed heteroaromatic hydrocarbons comprising only sulfur in the heteroaromatic polycondensed ring system, e.g. benzothiophene
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2101/00—Properties of the organic materials covered by group H10K85/00
    • H10K2101/10—Triplet emission
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2101/00—Properties of the organic materials covered by group H10K85/00
    • H10K2101/40—Interrelation of parameters between multiple constituent active layers or sublayers, e.g. HOMO values in adjacent layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2101/00—Properties of the organic materials covered by group H10K85/00
    • H10K2101/90—Multiple hosts in the emissive layer
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/30—Coordination compounds
    • H10K85/341—Transition metal complexes, e.g. Ru(II)polypyridine complexes
    • H10K85/342—Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising iridium

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Optics & Photonics (AREA)
  • Electroluminescent Light Sources (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Led Devices (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)

Abstract

The present disclosure provides novel compounds and organic light emitting devices comprising the same.

Description

Novel compound and organic light emitting device comprising the same
Technical Field
Cross Reference to Related Applications
The present application claims priority or equity from korean patent application No. 10-2018-0148563, which was filed on the date of 2018, 11, 27, and korean patent application No. 10-2019-0153522, which was filed on the date of 2019, 11, 26, to the korean intellectual property office, the disclosures of which are incorporated herein by reference in their entirety.
The present disclosure relates to novel compounds and organic light emitting devices comprising the same.
Background
In general, an organic light emitting phenomenon refers to a phenomenon in which electric energy is converted into light energy by using an organic material. An organic light emitting device using the organic light emitting phenomenon has characteristics such as a wide viewing angle, excellent contrast, a fast response time, excellent brightness, driving voltage, and response speed, and thus many researches have been conducted.
The organic light emitting device generally has a structure including an anode, a cathode, and an organic material layer interposed between the anode and the cathode. The organic material layer generally has a multi-layered structure including different materials to improve efficiency and stability of the organic light emitting device, for example, the organic material layer may be formed of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and the like. In the structure of the organic light emitting device, if a voltage is applied between two electrodes, holes are injected from an anode into an organic material layer and electrons are injected from a cathode into the organic material layer, excitons are formed when the injected holes and electrons meet each other, and light is emitted when the excitons fall to a ground state again.
There is a continuing need to develop new materials for organic materials used in organic light emitting devices as described above.
[ Prior Art literature ]
[ patent literature ]
(patent document 1) Korean unexamined patent publication No. 10-2000-0051826
Disclosure of Invention
Technical problem
It is an object of the present disclosure to provide novel compounds and organic light emitting devices comprising the same.
Technical proposal
In one aspect of the present disclosure, there is provided a compound represented by the following chemical formula 1:
[ chemical formula 1]
Wherein, in the chemical formula 1,
X 1 to X 6 Each independently CH or N, provided that X 1 To X 6 At least one of which is N,
Ar 1 to Ar 4 Each independently is a substituted or unsubstituted C 6-60 Aryl, provided that Ar 1 To Ar 4 At least one of them is C containing deuterium as a substituent 6-60 An aryl group,
R 1 is hydrogen; deuterium; substituted or unsubstituted C 6-60 An aryl group; or substituted or unsubstituted C comprising any one or more selected from N, O and S 2-60 Heteroaryl, and
n is an integer from 0 to 8.
In another aspect of the present disclosure, there is provided an organic light emitting device including: a first electrode; a second electrode disposed opposite to the first electrode; and one or more organic material layers disposed between the first electrode and the second electrode, wherein one or more of the organic material layers includes a compound represented by chemical formula 1.
Advantageous effects
The compound represented by chemical formula 1 described above may be used as a material of an organic material layer of an organic light emitting device, and may improve efficiency, achieve a low driving voltage, and/or improve lifetime characteristics in the organic light emitting device. In particular, the compound represented by chemical formula 1 may be used as a hole injecting material, a hole transporting material, a hole injecting and transporting material, a light emitting material, an electron transporting material, or an electron injecting material.
Drawings
Fig. 1 shows an example of an organic light emitting device including a substrate 1, an anode 2, a light emitting layer 3, and a cathode 4.
Fig. 2 shows an example of an organic light emitting device including a substrate 1, an anode 2, a hole injection layer 5, a hole transport layer 6, an electron blocking layer 7, a light emitting layer 3, an electron transport layer 8, an electron injection layer 9, and a cathode 4.
Detailed Description
Hereinafter, embodiments of the present disclosure will be described in more detail to aid understanding of the present invention.
An embodiment of the present invention provides a compound represented by chemical formula 1.
As used herein, a symbolMeaning a bond to another substituent.
As used herein, the term "substituted or unsubstituted" means unsubstituted or substituted with one or more substituents selected from the group consisting of: deuterium; a halogen group; a nitrile group; a nitro group; a hydroxyl group; a carbonyl group; an ester group; an imide group; an amino group; a phosphine oxide group; an alkoxy group; an aryloxy group; alkylthio; arylthio; an alkylsulfonyl group; arylsulfonyl; a silyl group; a boron base; an alkyl group; cycloalkyl; alkenyl groups; an aryl group; an aralkyl group; aralkenyl; alkylaryl groups; an alkylamino group; an aralkylamine group; heteroaryl amine groups; an arylamine group; aryl phosphino; or a heterocyclic group comprising at least one of N, O and S atoms, or a substituent which is unsubstituted or linked via two or more of the substituents exemplified above. For example, a "substituent in which two or more substituents are linked" may be a biphenyl group. That is, biphenyl may also be aryl and may be interpreted as a substituent to which two phenyl groups are linked.
In the present specification, the number of carbon atoms of the carbonyl group is not particularly limited, but is preferably 1 to 40. Specifically, the carbonyl group may be a group having the following structural formula, but is not limited thereto.
In the present specification, the ester group may have a structure in which oxygen of the ester group may be substituted with a linear, branched or cyclic alkyl group having 1 to 25 carbon atoms, or an aryl group having 6 to 25 carbon atoms. Specifically, the ester group may be a group having the following structural formula, but is not limited thereto.
In the present specification, the number of carbon atoms of the imide group is not particularly limited, but is preferably 1 to 25. Specifically, the imide group may be a group having the following structural formula, but is not limited thereto.
In the present specification, the silyl group specifically includes, but is not limited to, trimethylsilyl group, triethylsilyl group, t-butyldimethylsilyl group, vinyldimethylsilyl group, propyldimethylsilyl group, triphenylsilyl group, diphenylsilyl group, phenylsilyl group, and the like.
In the present specification, the boron group specifically includes trimethylboron group, triethylboron group, t-butyldimethylboroyl group, triphenylboron group and phenylboron group, but is not limited thereto.
In the present specification, examples of the halogen group include fluorine, chlorine, bromine, or iodine.
In the present specification, the alkyl group may be straight or branched, and the number of carbon atoms thereof is not particularly limited, but is preferably 1 to 40. According to one embodiment, the alkyl group has a carbon number of 1 to 20. According to another embodiment, the alkyl group has a carbon number of 1 to 10. According to another embodiment, the alkyl group has a carbon number of 1 to 6. Specific examples of the alkyl group include, but are not limited to, methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3-dimethylbutyl, 2-ethylbutyl, heptyl, n-heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2-dimethylheptyl, 1-ethyl-propyl, 1-dimethyl-propyl, isohexyl, 4-methylhexyl, 5-methylhexyl and the like.
In the present specification, the alkenyl group may be straight or branched, and the number of carbon atoms thereof is not particularly limited, but is preferably 2 to 40. According to one embodiment, the alkenyl group has 2 to 20 carbon atoms. According to another embodiment, the alkenyl group has a carbon number of 2 to 10. According to yet another embodiment, the alkenyl group has a carbon number of 2 to 6. Specific examples thereof include vinyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-methyl-1-butenyl, 1, 3-butadienyl, allyl, 1-phenylvinyl-1-yl, 2-diphenylvinyl-1-yl, 2-phenyl-2- (naphthalen-1-yl) vinyl-1-yl, 2-bis (diphenyl-1-yl) vinyl-1-yl, stilbene, styryl and the like, but are not limited thereto.
In the present specification, the cycloalkyl group is not particularly limited, but the number of carbon atoms thereof is preferably 3 to 60. According to one embodiment, the cycloalkyl group has a carbon number of 3 to 30. According to another embodiment, the cycloalkyl group has a number of carbon atoms of 3 to 20. According to yet another embodiment, the cycloalkyl group has a number of carbon atoms of 3 to 6. Specific examples thereof include cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2, 3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2, 3-dimethylcyclohexyl, 3,4, 5-trimethylcyclohexyl, 4-t-butylcyclohexyl, cycloheptyl, cyclooctyl and the like, but are not limited thereto.
In the present specification, the aryl group is not particularly limited, but preferably has 6 to 60 carbon atoms, and may be a monocyclic aryl group or a polycyclic aryl group. According to one embodiment, the aryl group has a carbon number of 6 to 30. According to one embodiment, the aryl group has 6 to 20 carbon atoms. As the monocyclic aryl group, an aryl group may be phenyl, biphenyl, terphenyl, or the like, but is not limited thereto. Examples of polycyclic aryl groups include naphthyl, anthryl, phenanthryl, pyrenyl, perylenyl,A radical, a fluorenyl radical, etc., but is not limited thereto.
In the present specification, the fluorenyl group may be substituted, and two substituents may be linked to each other to form a spiro structure. In the case where the fluorenyl group is substituted, it may be formed Etc. However, the structure is not limited thereto.
In this specification, the heterocyclic group is a heterocyclic group containing one or more of O, N, si and S as a heteroatom, and the number of carbon atoms thereof is not particularly limited, but is preferably 2 to 60. Examples of heterocyclyl groups include thienyl, furyl, pyrrolyl, imidazolyl, thiazolyl,Azolyl, (-) -and (II) radicals>Diazolyl, triazolyl, pyridyl, bipyridyl, pyrimidinyl, triazinyl, acridinyl, pyridazinyl, pyrazinyl, quinolinyl, quinazolinyl, quinoxalinyl, phthalazinyl, pyridopyrimidinyl, pyridopyrazinyl, pyrazinopyrazinyl, isoquinolinyl, indolyl, carbazolyl, benzo->Oxazolyl, benzimidazolyl, benzothiazolyl, benzocarbazolyl, benzothienyl, dibenzothiophenyl, benzofuranyl, phenanthrolinyl, and i ∈ ->Oxazolyl, thiadiazolyl, benzothiazinyl, phenothiazinyl, dibenzofuranyl, and the like, but are not limited thereto.
In this specification, the aryl groups in the aralkyl group, the aralkenyl group, the alkylaryl group, and the arylamine group are the same as those of the foregoing examples of the aryl groups. In this specification, the alkyl groups in the aralkyl group, alkylaryl group, and alkylamino group are the same as those of the aforementioned examples of the alkyl group. In this specification, the heteroaryl group in the heteroarylamine group may be used as described for the aforementioned heterocyclic group. In this specification, alkenyl groups in aralkenyl groups are the same as the aforementioned examples of alkenyl groups. In the present specification, the foregoing description of aryl groups may be applied, except that arylene groups are divalent groups. In the present specification, the foregoing description of the heterocyclic group may be applied, except that the heteroarylene group is a divalent group. In the present specification, the foregoing description of aryl or cycloalkyl can be applied, except that the hydrocarbon ring is not a monovalent group but is formed by combining two substituents. In this specification, the foregoing description of the heterocyclic group may be applied, except that the heterocyclic ring is not a monovalent group but is formed by combining two substituents.
Preferably X 1 To X 6 Can each independently be CH or N, provided that X 1 To X 3 At least one of which may be N and X 4 To X 6 At least one of which may be N.
Preferably X 4 To X 6 Each may be N.
More preferably X 1 To X 3 Can each independently be CH or N, provided that X 1 To X 3 At least one of which may be N, and X 4 To X 6 Each may be N.
Preferably Ar 1 To Ar 4 May each independently be a substituted or unsubstituted C 6-20 Aryl, provided that Ar 1 To Ar 4 At least one of them may be C comprising deuterium as a substituent 6-20 Aryl groups.
Preferably Ar 1 To Ar 4 At least one of which may be a phenyl group substituted with five deuterium groups.
More preferably Ar 1 To Ar 4 May each independently be a substituted or unsubstituted C 6-20 Aryl, provided that Ar 1 To Ar 4 At least one of which may be a phenyl group substituted with five deuterium groups.
Most preferably Ar 1 To Ar 4 May each independently be phenyl, biphenyl, or phenyl substituted with five deuterium, provided that Ar 1 To Ar 4 At least one of which may be a phenyl group substituted with five deuterium groups.
Preferably, R 1 May be hydrogen; deuterium; substituted or unsubstituted C 6-20 An aryl group; or substituted or unsubstituted C comprising any one or more selected from N, O and S 2-20 Heteroaryl groups.
More preferably, R 1 May be hydrogen or phenyl.
Preferably, n may be an integer of 0 to 2.
Preferably, chemical formula 1 may be represented by any one of the following chemical formulas 1-1 to 1-7:
[ chemical formula 1-1]
[ chemical formulas 1-2]
[ chemical formulas 1-3]
[ chemical formulas 1-4]
[ chemical formulas 1-5]
[ chemical formulas 1-6]
[ chemical formulas 1-7]
Wherein, in chemical formulas 1-1 to 1-7,
X 1 to X 6 、Ar 1 To Ar 4 And R is 1 The same as those defined in chemical formula 1.
Representative examples of the compound represented by chemical formula 1 are as follows:
the compound represented by chemical formula 1 may be prepared, for example, according to a preparation method as shown in reaction scheme 1 or reaction scheme 2 below, and other remaining compounds may be prepared in a similar manner.
Reaction scheme 1
Reaction scheme 2
In schemes 1 and 2, X 1 To X 6 、Ar 1 To Ar 4 、R 1 And n is the same as that defined in chemical formula 1, Y 1 And Y 2 Each independently is halogen, and preferably Y 1 And Y 2 Each independently is chlorine or bromine.
Reaction scheme 1 is an amine substitution reaction, which is preferably carried out in the presence of a palladium catalyst and a base, and the reactive groups for the amine substitution reaction may be modified as known in the art. Furthermore, reaction scheme 2 is a Suzuki coupling reaction, which is preferably carried out in the presence of a palladium catalyst and a base, and the reactive groups for the Suzuki coupling reaction may be modified as known in the art. The above preparation method may be further embodied in the preparation examples described below.
Another embodiment of the present disclosure provides an organic light emitting device including the compound represented by chemical formula 1 above. As an example, there is provided an organic light emitting device including: a first electrode; a second electrode disposed opposite to the first electrode; and one or more organic material layers disposed between the first electrode and the second electrode, wherein one or more of the organic material layers includes a compound represented by chemical formula 1.
The organic material layer of the organic light emitting device of the present disclosure may have a single layer structure, or it may have a multi-layer structure in which two or more organic material layers are stacked. For example, the organic light emitting device of the present disclosure may have a structure including a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer, an electron transport layer, an electron injection layer, and the like as an organic material layer. However, the structure of the organic light emitting device is not limited thereto, and it may include a smaller number of organic material layers.
Further, the organic material layer may include a light emitting layer, wherein the light emitting layer may include a compound represented by chemical formula 1. In particular, the compounds according to the present disclosure may be used as hosts for light emitting layers.
Further, the organic material layer may include a hole transporting layer, a hole injecting layer, or a layer for simultaneously performing hole transport and hole injection, wherein the hole transporting layer, the hole injecting layer, or the layer for simultaneously performing hole transport and hole injection may include a compound represented by chemical formula 1.
Further, the organic material layer may include an electron transport layer, an electron injection layer, and a layer for simultaneously performing electron transport and electron injection, wherein the electron transport layer, the electron injection layer, and the layer for simultaneously performing electron transport and electron injection may include a compound represented by chemical formula 1.
Further, the organic material layer includes a light emitting layer and a hole transporting layer, wherein the light emitting layer and the hole transporting layer may include a compound represented by chemical formula 1.
Further, the organic light emitting device according to the present disclosure may be a normal organic light emitting device in which an anode, one or more organic material layers, and a cathode are sequentially stacked on a substrate. Further, the organic light emitting device according to the present disclosure may be an inverted organic light emitting device in which a cathode, one or more organic material layers, and an anode are sequentially stacked on a substrate. For example, fig. 1 and 2 illustrate the structure of an organic light emitting device according to one embodiment of the present disclosure.
Fig. 1 shows an example of an organic light emitting device including a substrate 1, an anode 2, a light emitting layer 3, and a cathode 4. In such a structure, the compound represented by chemical formula 1 may be included in the light emitting layer.
Fig. 2 shows an example of an organic light emitting device including a substrate 1, an anode 2, a hole injection layer 5, a hole transport layer 6, an electron blocking layer 7, a light emitting layer 3, an electron transport layer 8, an electron injection layer 9, and a cathode 4. In such a structure, the compound represented by chemical formula 1 may be included in one or more of a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer, an electron transport layer, and an electron injection layer.
The organic light emitting device according to the present disclosure may be manufactured by materials and methods known in the art, except that one or more of the organic material layers include a compound represented by chemical formula 1. In addition, when the organic light emitting device includes a plurality of organic material layers, the organic material layers may be formed of the same material or different materials.
For example, an organic light emitting device according to the present disclosure may be manufactured by sequentially stacking a first electrode, an organic material layer, and a second electrode on a substrate. In this case, the organic light emitting device may be manufactured by: a metal, a metal oxide having conductivity, or an alloy thereof is deposited on a substrate using a PVD (physical vapor deposition) method such as a sputtering method or an electron beam evaporation method to form an anode, an organic material layer including a hole injection layer, a hole transport layer, a light emitting layer, and an electron transport layer is formed on the anode, and then a material that can function as a cathode is deposited on the organic material layer. In addition to such a method, the organic light emitting device may be manufactured by sequentially depositing a cathode material, an organic material layer, and an anode material on a substrate.
In addition, in manufacturing an organic light emitting device, the compound represented by chemical formula 1 may be formed into an organic material layer by a solution coating method as well as a vacuum deposition method. Here, the solution coating method means spin coating, dip coating, knife coating, ink jet printing, screen printing, spray method, roll coating, and the like, but is not limited thereto.
In addition to such a method, the organic light emitting device may be manufactured by sequentially depositing a cathode material, an organic material layer, and an anode material on a substrate (international publication WO 2003/012890). However, the manufacturing method is not limited thereto.
As an example, the first electrode is an anode and the second electrode is a cathode, or alternatively, the first electrode is a cathode and the second electrode is an anode.
As the anode material, it is generally preferable to use a material having a large work function so that holes can be smoothly injected into the organic material layer. Specific examples of the anode material include: metals such as vanadium, chromium, copper, zinc, and gold, or alloys thereof; metal oxides such as zinc oxide, indium Tin Oxide (ITO), and Indium Zinc Oxide (IZO); combinations of metals and oxides, e.g. ZnO, al or SnO 2 Sb; conductive polymers, e.g. poly (3-methylthiophene), poly [3,4- (ethylene-1, 2-dioxy) thiophene ](PEDOT), polypyrrole and polyaniline; etc., but is not limited thereto.
As the cathode material, it is generally preferable to use a material having a small work function so that electrons can be easily injected into the organic material layer. Specific examples of the cathode material include: metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, and lead, or alloys thereof; multilayer structural materials, e.g. LiF/Al or LiO 2 Al; etc., but is not limited thereto.
The hole injection layer is a layer for injecting holes from the electrode, and the hole injection material is preferably a compound of: it has a capability of transporting holes, and thus has an effect of injecting holes in an anode and has an excellent hole injection effect to a light emitting layer or a light emitting material, prevents excitons generated in the light emitting layer from moving to an electron injection layer or an electron injection material, and has an excellent capability of forming a thin film. Preferably, the HOMO (highest occupied molecular orbital) of the hole injection material is between the work function of the anode material and the HOMO of the surrounding organic material layer. Specific examples of the hole injection material include metalloporphyrin, oligothiophene, arylamine-based organic material, hexanitrile hexaazabenzophenanthrene-based organic material, quinacridone-based organic material, perylene-based organic material, anthraquinone, polyaniline-based and polythiophene-based conductive polymer, and the like, but are not limited thereto.
The hole transporting layer is a layer that receives holes from the hole injecting layer and transports the holes to the light emitting layer, and it is suitably a material having a large hole mobility that can receive holes from the anode or the hole injecting layer and transfer the holes to the light emitting layer. Specific examples thereof include an arylamine-based organic material, a conductive polymer, a block copolymer in which a conjugated moiety and a non-conjugated moiety are simultaneously present, and the like, but are not limited thereto.
The electron blocking layer is a layer provided between the hole transport layer and the light emitting layer to prevent electrons injected from the cathode from being transferred to the hole transport layer without being recombined in the light emitting layer, and may also be referred to as an electron suppressing layer. The electron blocking layer is preferably a material having a smaller electron affinity than the electron transport layer.
The luminescent material is preferably such a material: which can receive holes and electrons respectively transferred from the hole transport layer and the electron transport layer and combine the holes and electrons to emit light in the visible light region and have good quantum efficiency for fluorescence or phosphorescence. Specific examples of the light emitting material include: 8-hydroxy-quinoline aluminum complex (Alq 3 ) The method comprises the steps of carrying out a first treatment on the surface of the Carbazole-based compounds; a dimeric styryl compound; BAlq; 10-hydroxybenzoquinoline-metal compounds; based on benzo Azole and benzene basedBenzothiazole and benzimidazole-based compounds; poly (p-phenylene vinylene) (PPV) based polymers; a spiro compound; polyfluorene; rubrene; etc., but is not limited thereto.
The light emitting layer may include a host material and a dopant material. The host material may be a fused aromatic ring derivative, a heterocyclic ring-containing compound, or the like. Specific examples of the condensed aromatic ring derivative include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, fluoranthene compounds, and the like. Examples of the heterocycle-containing compound include carbazole derivatives, dibenzofuran derivatives, ladder-type furan compounds, pyrimidine derivatives, and the like, but are not limited thereto. Preferably, the compound represented by chemical formula 1 may be included as a host material.
Examples of dopant materials include aromatic amine derivatives, styrylamine compounds, boron complexes, fluoranthene compounds, metal complexes, and the like. Specifically, the aromatic amine derivative is a substituted or unsubstituted fused aromatic ring derivative having an arylamino group, and examples thereof include pyrene, anthracene having an arylamino group,Bisindenopyrene, and the like. Styrylamine compounds are compounds in which at least one arylvinyl group is substituted in a substituted or unsubstituted arylamine, wherein one or two or more substituents selected from the group consisting of aryl, silyl, alkyl, cycloalkyl, and arylamino groups are substituted or unsubstituted. Specific examples thereof include styrylamine, styrylenediamine, styrylenetriamine, styrylenetetramine, and the like, but are not limited thereto. Further, the metal complex includes iridium complex, platinum complex, and the like, but is not limited thereto.
The electron transport layer is a layer that receives electrons from the electron injection layer and transports the electrons to the light emitting layer, and the electron transport material is suitably such a material: which can well receive electrons from the cathode and transfer the electrons to the light emitting layer, and has a large electron mobility. Specific examples of the electron transport material include: al complexes of 8-hydroxyquinoline; comprising Alq 3 Is a complex of (a) and (b); an organic radical compound; hydroxyflavone-metal complexes; etc., but is not limited thereto. The electron transport layer may be used with any desired cathode material as used according to the related art. In particular, suitable examples of cathode materials are typical materials having a low work function followed by an aluminum layer or a silver layer. Specific examples thereof include cesium, barium, calcium, ytterbium and samarium, in each case followed by an aluminum layer or a silver layer.
The electron injection layer is a layer that injects electrons from an electrode, and is preferably a compound that: it has an ability to transport electrons, an effect of injecting electrons from a cathode and an excellent effect of injecting electrons into a light emitting layer or a light emitting material, prevents excitons generated by the light emitting layer from moving to a hole injecting layer, and also has an excellent ability to form a thin film. Specific examples of the electron injection layer include fluorenone, anthraquinone dimethane, diphenoquinone, thiopyran dioxide, Azole,/->Diazoles, triazoles, imidazoles, perylenetetracarboxylic acids, fluorenylenemethanes, anthrones, and the like, and derivatives thereof; a metal complex compound; a nitrogen-containing 5-membered ring derivative; etc., but is not limited thereto.
Examples of the metal complex compound include, but are not limited to, lithium 8-hydroxyquinoline, zinc bis (8-hydroxyquinoline), copper bis (8-hydroxyquinoline), manganese bis (8-hydroxyquinoline), aluminum tris (2-methyl-8-hydroxyquinoline), gallium tris (8-hydroxyquinoline), beryllium bis (10-hydroxybenzo [ h ] quinoline), zinc bis (2-methyl-8-quinoline) chlorogallium, gallium bis (2-methyl-8-quinoline) (o-cresol), aluminum bis (2-methyl-8-quinoline) (1-naphthol), gallium bis (2-methyl-8-quinoline) (2-naphthol), and the like.
The organic light emitting device according to the present disclosure may be of a front-side emission type, a rear-side emission type, or a double-side emission type, depending on the materials used.
In addition, the compound represented by chemical formula 1 may be contained in an organic solar cell or an organic transistor in addition to the organic light emitting device.
Hereinafter, embodiments will be described in more detail to aid understanding of the present invention. However, the following examples are provided for illustrative purposes only and are not intended to limit the scope of the present disclosure.
Preparation example
Preparation example 1: preparation of intermediate compounds T-1 to T-4
1) Preparation of intermediate compound T-1
Cyanuric chloride (50 g,273.3 mmol) and (phenyl-d 5) boric acid (34.7 g,273.3 mmol) were added to 1000ml of tetrahydrofuran under nitrogen, and the mixture was stirred and refluxed. Then, potassium carbonate (113.3 g,820 mmol) was dissolved in 113ml of water, added to the mixture and stirred well, and then tetrakis triphenylphosphine palladium (9.5 g,8.2 mmol) was added. After 3 hours of reaction, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was added to 1515ml of chloroform, dissolved and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by a silica gel column using chloroform and ethyl acetate to give compound T-1 (42.4 g, yield: 56%, MS: [ m+h ] +=278.1) as a white solid.
2) Preparation of intermediate compound T-2
2, 4-dichloro-6-phenyl-1, 3, 5-triazine (50 g,222.2 mmol) and (phenyl-d 5) boronic acid (28.2 g,222.2 mmol) were added to 1000ml of tetrahydrofuran under nitrogen atmosphere and the mixture was stirred and refluxed. Then, potassium carbonate (92.1 g,666.7 mmol) was dissolved in 92ml of water, and it was added to the mixture with stirring sufficiently, followed by the addition of tetrakis triphenylphosphine-palladium (7.7 g,6.7 mmol). After 1 hour of reaction, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was added to 1209ml of chloroform again, dissolved and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by a silica gel column using chloroform and ethyl acetate to give compound T-2 (44.1 g, yield: 73%, MS: [ m+h ] +=273.1) as a white solid.
3) Preparation of intermediate compound T-3
2- ([ 1,1' -biphenyl ] -4-yl) -4, 6-dichloro-1, 3, 5-triazine (50 g,166.1 mmol) and (phenyl-d 5) boronic acid (21.1 g,166.1 mmol) were added to 1000ml of tetrahydrofuran under nitrogen atmosphere and the mixture was stirred and refluxed. Then, potassium carbonate (68.9 g,498.3 mmol) was dissolved in 69ml of water, added to the mixture and stirred well, and then tetrakis triphenylphosphine palladium (5.8 g,5 mmol) was added. After 3 hours of reaction, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was added to 1156ml of chloroform, dissolved and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by a silica gel column using chloroform and ethyl acetate to give compound T-3 (43.4 g, yield: 75%, MS: [ m+h ] +=349.1) as a white solid.
4) Preparation of intermediate compound T-4
2- ([ 1,1' -biphenyl ] -3-yl) -4, 6-dichloro-1, 3, 5-triazine (50 g,166.1 mmol) and (phenyl-d 5) boronic acid (21.1 g,166.1 mmol) were added to 1000ml of tetrahydrofuran under nitrogen atmosphere and the mixture was stirred and refluxed. Then, potassium carbonate (68.9 g,498.3 mmol) was dissolved in 69ml of water, added to the mixture and stirred well, and then tetrakis triphenylphosphine palladium (5.8 g,5 mmol) was added. After 3 hours of reaction, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was added to 1156ml of chloroform, dissolved and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by a silica gel column using chloroform and ethyl acetate to give compound T-4 (44.5 g, yield: 77%, MS: [ m+h ] +=349.1) as a white solid.
Preparation example 2: preparation of intermediate compound sub 1
2-chloro-4, 6-diphenyl-1, 3, 5-triazine (30 g,112.3 mmol) and (3-chloro-4-fluorophenyl) boronic acid (19.5 g,112.3 mmol) were added to 600ml of tetrahydrofuran under a nitrogen atmosphere and the mixture was stirred and refluxed. Then, potassium carbonate (46.6 g,337 mmol) was dissolved in 47ml of water, which was added to the mixture and stirred well, followed by the addition of tetra-triphenylphosphine palladium (3.9 g,3.4 mmol). After 1 hour of reaction, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and then the organic layer was distilled. This was added to 811ml of chloroform again, dissolved and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by a silica gel column using chloroform and ethyl acetate to give compound 1-1 (26.4 g, yield: 65%, MS: [ m+h ] +=362.1) as a white solid.
Compound 1-1 (20 g,55.4 mmol) and bis (pinacolato) diboron (28.2 g,110.8 mmol) are added to 400ml of diboron under a nitrogen atmosphereThe mixture was stirred and refluxed with alkane. Then, potassium acetate (16 g,166.2 mmol) was added thereto with sufficient stirring, and palladium dibenzylidene acetone palladium (1 g,1.7 mmol) and tricyclohexylphosphine (0.9 g,3.3 mmol) were then added. After 7 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer was subjected to filtration treatment to remove salts, and then the filtered organic layer was distilled. It was added to 251ml of chloroform again, dissolved and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred, and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was recrystallized from chloroform and ethanol to obtain white solid compound 1-2 (22.3 g, yield: 89%, MS: [ M+H) ]+＝454.2)。/>
Compound 1-2 (30 g,66.2 mmol) and compound T-2 (18 g,66.2 mmol) were added to 600ml of tetrahydrofuran under nitrogen, and the mixture was stirred and refluxed. Then, potassium carbonate (27.4 g,198.6 mmol) was dissolved in 27ml of water, added to the mixture and stirred well, and then tetrakis triphenylphosphine palladium (2.3 g,2 mmol) was added. After 3 hours of reaction, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was added to 746ml of chloroform again, dissolved and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred, and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by a silica gel column using chloroform and ethyl acetate to give a white solid compound sub 1 (20.5 g, yield: 55%, MS: [ m+h ] += 564.2).
Preparation example 3: preparation of intermediate compound sub 2
2-chloro-4, 6-diphenyl-1, 3, 5-triazine (30 g,112.3 mmol) and (5-chloro-2-fluorophenyl) boronic acid (19.5 g,112.3 mmol) were added to 600ml of tetrahydrofuran under a nitrogen atmosphere and the mixture was stirred and refluxed. Then, potassium carbonate (46.6 g,337 mmol) was dissolved in 47ml of water, which was added to the mixture and stirred well, followed by the addition of tetra-triphenylphosphine palladium (3.9 g,3.4 mmol). After 1 hour of reaction, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. This was added to 811ml of chloroform again, dissolved and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred, and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by a silica gel column using chloroform and ethyl acetate to give compound 2-1 (30.8 g, yield: 76%, MS: [ m+h ] +=362.1) as a white solid.
Compound 2-1 (20 g,55.4 mmol) and 9H-carbazole (9.3 g,55.4 mmol) were added to 400ml of xylene under nitrogen, and the mixture was stirred and refluxed. Then, sodium t-butoxide (16 g,166.2 mmol) was added thereto with sufficient stirring, and bis (tri-t-butylphosphine) palladium (0.8 g,1.7 mmol) was then added thereto. After 5 hours of reaction, the reaction mixture was cooled to room temperature, and then the resulting solid was filtered. The solid was added to 844ml chloroform, dissolved and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred, and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by a silica gel column using chloroform and ethyl acetate to give compound 2-2 (20.8 g, yield: 74%, MS: [ m+h ] +=509.2) as a white solid.
Compound 2-2 (20 g,39.4 mmol) and bis (pinacolato) diboron (20 g,78.7 mmol) are added to 400ml of di under nitrogen atmosphereThe mixture was stirred and refluxed with alkane. Then, potassium acetate (11.3 g,118.1 mmol) was added thereto with sufficient stirring, and palladium dibenzylidene acetone palladium (0.7 g,1.2 mmol) and tricyclohexylphosphine (0.7 g,2.4 mmol) were then added. After 7 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer was subjected to filtration treatment to remove salts, and then the filtered organic layer was distilled. It was added to 178ml chloroform, dissolved and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred, and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was recrystallized from chloroform and ethanol to obtain white solid compound sub 2 (14.4 g, yield: 81%, MS: [ M+H ]+＝454.2)。
Preparation example 4: preparation of intermediate compound sub 3
2, 4-dibromo-1-fluorobenzene (50 g,98.4 mmol) and bis (pinacolato) diboron (50 g,196.8 mmol) were added to 1000ml of di under nitrogen atmosphereThe mixture was stirred and refluxed with alkane. Then, potassium acetate (28.4 g,295.2 mmol) was added thereto with sufficient stirring, and palladium dibenzylidene acetone palladium (1.7 g,3 mmol) and tricyclohexylphosphine (1.7 g,5.9 mmol) were then added. After 3 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer was subjected to filtration treatment to remove salts, and then the filtered organic layer was distilled. It was added to 343ml of chloroform, dissolved and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred, and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was recrystallized from chloroform and ethanol to obtain white solid compound 3-1 (30.2 g, yield: 88%, MS: [ M+H)]+＝349.2)。/>
Compound 3-1 (30 g,86.2 mmol) and compound T-1 (23.9 g,86.2 mmol) were added to 600ml of tetrahydrofuran under nitrogen, and the mixture was stirred and refluxed. Then, potassium carbonate (35.7 g,258.5 mmol) was dissolved in 36ml of water, which was added to the mixture and stirred well, and then tetrakis-triphenylphosphine palladium (3 g,2.6 mmol) was added. After 1 hour of reaction, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was added to 997ml of chloroform again, dissolved and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred, and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by a silica gel column using chloroform and ethyl acetate to give a white solid compound sub 3 (34.4 g, yield: 69%, MS: [ m+h ] +=579.3).
Preparation example 5: preparation of intermediate compound sub 4
Compound T-2 (50 g,183.8 mmol) and (5-chloro-2-fluorophenyl) boronic acid (32 g,183.8 mmol) were added to 1000ml of tetrahydrofuran under a nitrogen atmosphere and the mixture was stirred and refluxed. Then, potassium carbonate (76.2 g,551.3 mmol) was dissolved in 76ml of water, and it was added to the mixture with stirring well, and then tetrakis triphenylphosphine palladium (6.4 g,5.5 mmol) was added. After 3 hours of reaction, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and then the organic layer was distilled. This was added to 1346ml of chloroform, dissolved and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred, and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by a silica gel column using chloroform and ethyl acetate to give compound 4-1 (41.7 g, yield: 62%, MS: [ m+h ] += 367.1) as a white solid.
Compound 4-1 (20 g,54.6 mmol) and 2-phenyl-9H-carbazole (20.0 g,54.6 mmol) were added to 400ml of xylene under nitrogen, and the mixture was stirred and refluxed. Then, sodium t-butoxide (15.8 g,163.9 mmol) was added thereto with sufficient stirring, and bis (tri-t-butylphosphine) palladium (0.8 g,1.6 mmol) was then added thereto. After 1 hour of reaction, the reaction mixture was cooled to room temperature, and then the resultant solid was filtered. The solid was added to 966ml chloroform, dissolved and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred, and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by a silica gel column using chloroform and ethyl acetate to give compound 4-2 (21.9 g, yield: 68%, MS: [ m+h ] += 590.2) as a white solid.
Compound 4-2 (20 g,33.9 mmol) and bis (pinacolato) diboron (17.3 g,67.9 mmol) are added to 400ml of diboron under a nitrogen atmosphereThe mixture was stirred and refluxed with alkane. Then, potassium acetate (9.8 g,101.8 mmol) was added thereto with sufficient stirring, and palladium dibenzylidene acetone palladium (0.6 g,1 mmol) and tricyclohexylphosphine (0.6 g,2 mmol) were then added. After 7 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer was subjected to filtration treatment to remove salts, and then the filtered organic layer was distilled. It was added to 231ml chloroform again, dissolved and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred, and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was recrystallized from chloroform and ethanol to obtain white solid compound sub 4 (12.3 g, yield: 53%, MS: [ M+H]+＝682.4)。
Preparation example 6: preparation of intermediate compound sub 5
Compound T-1 (50 g,180.4 mmol) and (5-chloro-2-fluorophenyl) boronic acid (31.4 g,180.4 mmol) were added to 1000ml of tetrahydrofuran under a nitrogen atmosphere and the mixture was stirred and refluxed. Then, potassium carbonate (74.8 g,541.3 mmol) was dissolved in 75ml of water, and it was added to the mixture with stirring sufficiently, followed by the addition of tetrakis-triphenylphosphine palladium (6.3 g,5.4 mmol). After 3 hours of reaction, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was added to 1339ml of chloroform, dissolved and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by a silica gel column using chloroform and ethyl acetate to give compound 5-1 (39.5 g, yield: 59%, MS: [ m+h ] +=372.1) as a white solid.
Compound 5-1 (30 g,80.8 mmol) and 4-phenyl-9H-carbazole (30 g,80.8 mmol) were added to 600ml of xylene under nitrogen, and the mixture was stirred and refluxed. Then, sodium t-butoxide (23.3 g,242.5 mmol) was added thereto with sufficient stirring, and bis (tri-t-butylphosphine) palladium (1.2 g,2.4 mmol) was then added thereto. After 1 hour of reaction, the reaction mixture was cooled to room temperature, and then the resultant solid was filtered. The solid was added to 1441ml chloroform, dissolved and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred, and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by a silica gel column using chloroform and ethyl acetate to give compound 5-2 (31.2 g, yield: 65%, MS: [ m+h ] += 595.2) as a white solid.
Compound 5-2 (20 g,33.7 mmol) and bis (pinacolato) diboron (17.1 g,67.3 mmol) are added to 400ml of diboron under a nitrogen atmosphereThe mixture was stirred and refluxed with alkane. Then, potassium acetate (9.7 g,101 mmol) was added thereto with sufficient stirring, and palladium dibenzylidene acetone palladium (0.6 g,1 mmol) and tricyclohexylphosphine (0.6 g,2 mmol) were then added. After 5 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer was subjected to filtration treatment to remove salts, and then the filtered organic layer was distilled. It was added to 231ml chloroform again, dissolved and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred, and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was recrystallized from chloroform and ethanol to obtain white solid compound sub 5 (13.4 g, yield: 58%, MS: [ M+H) ]+＝687.4)。
Preparation example 7: preparation of Compound 1
Compound sub 1 (10 g,17.8 mmol) and 9H-carbazole (3 g,17.8 mmol) were added to 200ml dimethylformamide under nitrogen atmosphere and the mixture was stirred and refluxed. Then, sodium t-butoxide (11.3 g,53.3 mmol) was added thereto with sufficient stirring, and bis (tri-t-butylphosphine) palladium (0.3 g,0.5 mmol) was then added thereto. After 6 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer was subjected to filtration treatment to remove salts, and then the filtered organic layer was distilled. It was added to 126ml of chloroform, dissolved and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred, and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by a silica gel column using chloroform and ethyl acetate to obtain yellow solid compound 1 (7.2 g, yield: 57%, MS: [ m+h ] += 711.3).
Preparation example 8: preparation of Compound 2
Compound sub 1 (10 g,17.8 mmol) and 1-phenyl-9H-carbazole (4.3 g,17.8 mmol) were added to 200ml dimethylformamide under nitrogen atmosphere and the mixture was stirred and refluxed. Then, sodium t-butoxide (11.3 g,53.3 mmol) was added thereto with sufficient stirring, and bis (tri-t-butylphosphine) palladium (0.3 g,0.5 mmol) was then added thereto. After 7 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer was subjected to filtration treatment to remove salts, and then the filtered organic layer was distilled. It was added to 140ml of chloroform again, dissolved and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred, and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by a silica gel column using chloroform and ethyl acetate to give compound 2 (7.7 g, yield: 55%, MS: [ m+h ] +=787.3) as a yellow solid.
Preparation example 9: preparation of Compound 3
Compound sub 1 (10 g,17.8 mmol) and 2-phenyl-9H-carbazole (8.9 g,17.8 mmol) were added to 200ml dimethylformamide under nitrogen atmosphere and the mixture was stirred and refluxed. Then, sodium t-butoxide (11.3 g,53.3 mmol) was added thereto with sufficient stirring, and bis (tri-t-butylphosphine) palladium (0.3 g,0.5 mmol) was then added thereto. After 4 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer was subjected to filtration treatment to remove salts, and then the filtered organic layer was distilled. It was added to 140ml of chloroform again, dissolved and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred, and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by a silica gel column using chloroform and ethyl acetate to give compound 3 (10.9 g, yield: 78%, MS: [ m+h ] +=787.3) as a yellow solid.
Preparation example 10: preparation of Compound 4
Compound sub 1 (10 g,17.8 mmol) and 3-phenyl-9H-carbazole (10.7 g,17.8 mmol) were added to 200ml dimethylformamide under nitrogen atmosphere and the mixture was stirred and refluxed. Then, sodium t-butoxide (11.3 g,53.3 mmol) was added thereto with sufficient stirring, and bis (tri-t-butylphosphine) palladium (0.3 g,0.5 mmol) was then added thereto. After 6 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer was subjected to filtration treatment to remove salts, and then the filtered organic layer was distilled. It was added to 140ml of chloroform again, dissolved and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred, and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by a silica gel column using chloroform and ethyl acetate to give compound 4 (8 g, yield: 57%, MS: [ m+h ] +=787.3) as a yellow solid.
Preparation example 11: preparation of Compound 5
Compound sub 1 (10 g,17.8 mmol) and 4-phenyl-9H-carbazole (12.4 g,17.8 mmol) were added to 200ml dimethylformamide under nitrogen atmosphere and the mixture was stirred and refluxed. Then, sodium t-butoxide (11.3 g,53.3 mmol) was added thereto with sufficient stirring, and bis (tri-t-butylphosphine) palladium (0.3 g,0.5 mmol) was then added thereto. After 5 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer was subjected to filtration treatment to remove salts, and then the filtered organic layer was distilled. It was added to 160ml of chloroform again, dissolved and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred, and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by a silica gel column using chloroform and ethyl acetate to give compound 5 (11.5 g, yield: 72%, MS: [ m+h ] +=901) as a yellow solid.
Preparation example 12: preparation of Compound 6
Compound sub 1 (10 g,17.8 mmol) and 2, 7-diphenyl-9H-carbazole (5.7 g,17.8 mmol) were added to 200ml dimethylformamide under nitrogen atmosphere and the mixture was stirred and refluxed. Then, sodium t-butoxide (11.3 g,53.3 mmol) was added thereto with sufficient stirring, and bis (tri-t-butylphosphine) palladium (0.3 g,0.5 mmol) was then added thereto. After 3 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer was subjected to filtration treatment to remove salts, and then the filtered organic layer was distilled. It was added to 153ml chloroform again, dissolved and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred, and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by a silica gel column using chloroform and ethyl acetate to obtain yellow solid compound 6 (11.6 g, yield: 76%, MS: [ m+h ] +=863.4).
Preparation example 13: preparation of Compound 7
Compound sub 1 (10 g,17.8 mmol) and 3, 6-diphenyl-9H-carbazole (5.7 g,17.8 mmol) were added to 200ml dimethylformamide under nitrogen atmosphere and the mixture was stirred and refluxed. Then, sodium t-butoxide (11.3 g,53.3 mmol) was added thereto with sufficient stirring, and bis (tri-t-butylphosphine) palladium (0.3 g,0.5 mmol) was then added thereto. After 3 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer was subjected to filtration treatment to remove salts, and then the filtered organic layer was distilled. It was added to 153ml chloroform again, dissolved and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred, and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by a silica gel column using chloroform and ethyl acetate to give compound 7 (10.9 g, yield: 71%, MS: [ m+h ] +=863.4) as a yellow solid.
Preparation example 14: preparation of Compound 8
Compound sub 2 (50 g,83.3 mmol) and compound T-2 (22.7 g,83.3 mmol) were added to 1000ml of tetrahydrofuran under nitrogen atmosphere and the mixture was stirred and refluxed. Then, potassium carbonate (34.5 g,249.9 mmol) was dissolved in 35ml of water, which was added to the mixture and stirred well, and then tetrakis-triphenylphosphine palladium (2.9 g,2.5 mmol) was added. After 3 hours of reaction, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was added to 1183ml of chloroform, dissolved and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by a silica gel column using chloroform and ethyl acetate to give compound 8 (39.6 g, yield: 67%, MS: [ M+H) as a white solid ] + ＝711.3)。
Preparation example 15: preparation of Compound 9
Compound sub 2 (50 g,83.3 mmol) and compound T-3 (29 g,83.3 mmol) were added to 1000ml of tetrahydrofuran under nitrogen, and the mixture was stirred and refluxed. Then, potassium carbonate (34.5 g,249.9 mmol) was dissolved in 35ml of water, which was added to the mixture and stirred well, and then tetrakis-triphenylphosphine palladium (2.9 g,2.5 mmol) was added. After 3 hours of reaction, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was added to 1310ml of chloroform again, dissolved and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by a silica gel column using chloroform and ethyl acetate to give compound 9 (43.2 g, yield: 66%, MS: [ m+h ] +=787.3) as a white solid.
Preparation example 16: preparation of Compound 10
Compound sub 2 (50 g,83.3 mmol) and compound T-4 (29 g,83.3 mmol) were added to 1000ml of tetrahydrofuran under nitrogen, and the mixture was stirred and refluxed. Then, potassium carbonate (34.5 g,249.9 mmol) was dissolved in 35ml of water, which was added to the mixture and stirred well, and then tetrakis-triphenylphosphine palladium (2.9 g,2.5 mmol) was added. After 3 hours of reaction, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was added to 1310ml of chloroform again, dissolved and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by a silica gel column using chloroform and ethyl acetate to give compound 10 (51.7 g, yield: 79%, MS: [ m+h ] +=787.3) as a white solid.
Preparation example 17: preparation of Compound 11
Compound sub 3 (10 g,17.3 mmol) and 9H-carbazole (2.9 g,17.3 mmol) were added to 200ml dimethylformamide under nitrogen atmosphere and the mixture was stirred and refluxed. Then, sodium t-butoxide (11 g,51.9 mmol) was added thereto with sufficient stirring, and bis (tri-t-butylphosphine) palladium (0.3 g,0.5 mmol) was then added thereto. After 6 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer was subjected to filtration treatment to remove salts, and then the filtered organic layer was distilled. It was added to 149ml of chloroform, dissolved and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred, and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by a silica gel column using chloroform and ethyl acetate to give compound 11 (7.6 g, yield: 51%, MS: [ m+h ] +=863.4) as a yellow solid.
Preparation example 18: preparation of Compound 12
Compound sub 3 (10 g,17.3 mmol) and 2-phenyl-9H-carbazole (4.2 g,17.3 mmol) were added to 200ml dimethylformamide under nitrogen atmosphere and the mixture was stirred and refluxed. Then, sodium t-butoxide (11 g,51.9 mmol) was added thereto with sufficient stirring, and bis (tri-t-butylphosphine) palladium (0.3 g,0.5 mmol) was then added thereto. After 5 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer was subjected to filtration treatment to remove salts, and then the filtered organic layer was distilled. It was added to 139ml of chloroform again, dissolved and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred, and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by a silica gel column using chloroform and ethyl acetate to obtain compound 12 (7.8 g, yield: 56%, MS: [ m+h ] +=802.4) as a yellow solid.
Preparation example 19: preparation of Compound 13
Compound sub 3 (10 g,17.3 mmol) and 3-phenyl-9H-carbazole (4.2 g,17.3 mmol) were added to 200ml dimethylformamide under nitrogen atmosphere and the mixture was stirred and refluxed. Then, sodium t-butoxide (11 g,51.9 mmol) was added thereto with sufficient stirring, and bis (tri-t-butylphosphine) palladium (0.3 g,0.5 mmol) was then added thereto. After 7 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer was subjected to filtration treatment to remove salts, and then the filtered organic layer was distilled. It was added to 139ml of chloroform again, dissolved and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred, and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by a silica gel column using chloroform and ethyl acetate to obtain yellow solid compound 13 (10.4 g, yield: 75%, MS: [ m+h ] +=802.4).
Preparation example 20: preparation of Compound 14
Compound sub 3 (10 g,17.3 mmol) and 4-phenyl-9H-carbazole (4.2 g,17.3 mmol) were added to 200ml dimethylformamide under nitrogen atmosphere and the mixture was stirred and refluxed. Then, sodium t-butoxide (11 g,51.9 mmol) was added thereto with sufficient stirring, and bis (tri-t-butylphosphine) palladium (0.3 g,0.5 mmol) was then added thereto. After 6 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer was subjected to filtration treatment to remove salts, and then the filtered organic layer was distilled. It was added to 139ml of chloroform again, dissolved and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred, and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by a silica gel column using chloroform and ethyl acetate to give compound 14 (10.3 g, yield: 74%, MS: [ m+h ] +=802.4) as a yellow solid.
Preparation example 21: preparation of Compound 15
Compound sub 4 (10 g,14.7 mmol) and 2-bromo-4, 6-diphenylpyridine (4.5 g,14.7 mmol) were added to 200ml of tetrahydrofuran under nitrogen atmosphere and the mixture was stirred and refluxed. Then, potassium carbonate (6.1 g,44 mmol) was dissolved in 6ml of water, added to the mixture and stirred well, and then tetrakis-triphenylphosphine palladium (0.5 g,0.4 mmol) was added. After 2 hours of reaction, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was added to 230ml chloroform again, dissolved and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was recrystallized from chloroform and ethyl acetate to obtain yellow solid compound 15 (8.9 g, yield: 77%, MS: [ m+h ] += 785.3).
Preparation example 22: preparation of Compound 16
Compound sub 4 (10 g,14.7 mmol) and 2-chloro-4, 6-diphenylpyrimidine (3.9 g,14.7 mmol) were added to 200ml tetrahydrofuran under nitrogen atmosphere and the mixture was stirred and refluxed. Then, potassium carbonate (6.1 g,44 mmol) was dissolved in 6ml of water, added to the mixture and stirred well, and then tetrakis-triphenylphosphine palladium (0.5 g,0.4 mmol) was added. After 3 hours of reaction, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was added to 230ml chloroform again, dissolved and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was recrystallized from chloroform and ethyl acetate to obtain yellow solid compound 16 (8.5 g, yield: 74%, MS: [ m+h ] += 786.3).
Preparation example 23: preparation of Compound 17
Compound sub 4 (10 g,14.7 mmol) and 4-chloro-2, 6-diphenylpyrimidine (3.9 g,14.7 mmol) were added to 200ml tetrahydrofuran under nitrogen atmosphere and the mixture was stirred and refluxed. Then, potassium carbonate (6.1 g,44 mmol) was dissolved in 6ml of water, added to the mixture and stirred well, and then tetrakis-triphenylphosphine palladium (0.5 g,0.4 mmol) was added. After 1 hour of reaction, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was added to 230ml chloroform again, dissolved and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was recrystallized from chloroform and ethyl acetate to obtain yellow solid compound 17 (9 g, yield: 78%, MS: [ m+h ] += 786.3).
Preparation example 24: preparation of Compound 18
Compound sub 5 (10 g,14.6 mmol) and 2-chloro-4, 6-diphenyl-1, 3, 5-triazine (3.9 g,14.6 mmol) were added to 200ml tetrahydrofuran under nitrogen atmosphere and the mixture was stirred and refluxed. Then, potassium carbonate (6 g,43.7 mmol) was dissolved in 6ml of water, which was added to the mixture and stirred well, and then tetrakis-triphenylphosphine palladium (0.5 g,0.4 mmol) was added. After 3 hours of reaction, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was added to 231ml chloroform again, dissolved and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was recrystallized from chloroform and ethyl acetate to obtain yellow solid compound 18 (8.5 g, yield: 74%, MS: [ m+h ] += 792.4).
Preparation example 25: preparation of Compound 19
Compound sub 5 (10 g,14.6 mmol) and 4-chloro-2, 6-diphenylpyrimidine (3.9 g,14.6 mmol) were added to 200ml tetrahydrofuran under nitrogen atmosphere and the mixture was stirred and refluxed. Then, potassium carbonate (6 g,43.7 mmol) was dissolved in 6ml of water, which was added to the mixture and stirred well, and then tetrakis-triphenylphosphine palladium (0.5 g,0.4 mmol) was added. After 2 hours of reaction, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was added to 230ml chloroform again, dissolved and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was recrystallized from chloroform and ethyl acetate to obtain yellow solid compound 19 (8.6 g, yield: 75%, MS: [ m+h ] += 791.4).
Preparation example 26: preparation of Compound 20
Compound sub 5 (10 g,14.6 mmol) and 2-chloro-4, 6-diphenylpyrimidine (3.9 g,14.6 mmol) were added to 200ml tetrahydrofuran under nitrogen atmosphere and the mixture was stirred and refluxed. Then, potassium carbonate (6 g,43.7 mmol) was dissolved in 6ml of water, which was added to the mixture and stirred well, and then tetrakis-triphenylphosphine palladium (0.5 g,0.4 mmol) was added. After 1 hour of reaction, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was added to 230ml chloroform again, dissolved and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was recrystallized from chloroform and ethyl acetate to obtain yellow solid compound 20 (9.2 g, yield: 80%, MS: [ m+h ] += 791.4).
Examples (example)
Example 1
Coated with a coating having a thickness ofThe glass substrate as a thin film was put into distilled water in which a cleaning agent was dissolved, and subjected to ultrasonic cleaning. At this time, a product manufactured by Fischer co. Was used as a detergent, and as distilled water, distilled water filtered twice using a filter manufactured by Millipore co. After washing the ITO for 30 minutes, ultrasonic washing was repeated twice using distilled water for 10 minutes. After the washing with distilled water was completed, the substrate was ultrasonically washed with isopropyl alcohol, acetone and methanol solvents, dried, and then transferred to a plasma washer. In addition, the substrate was cleaned using oxygen plasma for 5 minutes and then transferred to a vacuum depositor.
On the ITO transparent electrode thus prepared, the following compounds HI-1 to HI were thermally vacuum depositedTo form a hole injection layer. Thermal vacuum deposition of the following compounds HT-1 to +.>To form a hole transport layer, and vacuum depositing the following compounds HT-2 to +.>To form an electron blocking layer. Compound 1, the following compound YGH-1, and the following phosphorescent dopant YGD-1 prepared in the previous preparation example 7 were co-deposited on the HT-2 deposition layer at a weight ratio of 44:44:12 to form a thickness +. >Is provided. Vacuum depositing the following compounds ET-1 to->To form an electron transport layer, and vacuum depositing the following compounds ET-2 and Li on the electron transport layer in a weight ratio of 98:2 to form a thickness +.>Electron injection layer of (a) is provided. Depositing aluminum on the electron injection layer to +.>To form a cathode. />
In the above process, the vapor deposition rate of the organic material is maintained atTo-> The deposition rate of aluminum is kept at +.>And the vacuum degree during deposition is maintained at 1×10 -7 To 5X 10 -8 And (5) a bracket.
Examples 2 to 20
An organic light-emitting device was manufactured in the same manner as in example 1, except that the compound shown in table 1 below was used instead of the compound 1 of preparation example 7 in example 1.
Comparative examples 1 and 2
An organic light-emitting device was manufactured in the same manner as in example 1, except that the compound shown in table 1 below was used instead of the compound 1 of preparation example 7 in example 1. In table 1, compounds CE1 and CE2 are as follows.
Experimental example
At 10mA/cm 2 The voltage and efficiency of the organic light emitting devices manufactured in examples and comparative examples were measured at a current density of 50mA/cm 2 The lifetime is measured at the current density of (2). The results are shown in table 1 below. At this time, LT 95 Meaning the time required for the brightness to decrease to 95% of the original brightness.
TABLE 1
As shown in table 1 above, when the compound of the present disclosure was used as a light-emitting layer material, it was determined that it exhibited excellent efficiency and lifetime compared to the comparative example. This is thought to be due to deuterium further substituting the derivative, thereby improving the orbital stability for electron transport in the molecule.
On the other hand, when examples 1 to 4 and example 5, or examples 11 to 13 and example 14 were compared, it was confirmed that in the case where the organic light-emitting device included the compound having the substituent at the position 4 of the parent carbazole as a main body, the lifetime characteristics were significantly improved. It can be inferred from this that when position 4 of carbazole is substituted, the orbital stability is significantly improved and the lifetime characteristics are improved.
[ reference numerals ]
1: substrate 2: anode
3: light emitting layer 4: cathode electrode
5: hole injection layer 6: hole transport layer
7: electron blocking layer 8: electron transport layer
9: electron injection layer

Claims (7)

1. A compound represented by the following chemical formula 1:
[ chemical formula 1]
Wherein, in the chemical formula 1,
X 1 to X 6 Each independently CH or N, provided that X 1 To X 3 At least one of which is N and X 4 To X 6 At least one of which is N,
Ar 1 to Ar 4 Each independently is C 6-30 Aryl, provided that Ar 1 To Ar 4 At least one of which is phenyl substituted with five deuterium,
R 1 is hydrogen; deuterium; or C 6-30 Aryl, and
n is an integer of 0 to 2,
with the proviso that the following compounds are excluded:
2. the compound according to claim 1, wherein
X 4 To X 6 Each is N.
3. The compound according to claim 1, wherein
Ar 1 To Ar 4 Each independently is phenyl, biphenyl, or phenyl substituted with five deuterium, provided that Ar 1 To Ar 4 At least one of which is a phenyl group substituted with five deuterium groups.
4. The compound according to claim 1, wherein
R 1 Is hydrogen or phenyl.
5. The compound according to claim 1, wherein
The chemical formula 1 is represented by any one of the following chemical formulas 1-1 to 1-7:
[ chemical formula 1-1]
[ chemical formulas 1-2]
[ chemical formulas 1-3]
[ chemical formulas 1-4]
[ chemical formulas 1-5]
[ chemical formulas 1-6]
[ chemical formulas 1-7]
Wherein, in chemical formulas 1-1 to 1-7, X 1 To X 6 、Ar 1 To Ar 4 And R is 1 As defined in claim 1.
6. The compound according to claim 1, wherein
The compound represented by chemical formula 1 is any one selected from the group consisting of:
7. an organic light emitting device comprising: a first electrode; a second electrode disposed opposite to the first electrode; and one or more organic material layers disposed between the first electrode and the second electrode, wherein one or more of the organic material layers comprises the compound according to any one of claims 1 to 6.
CN201980059738.6A 2018-11-27 2019-11-27 Novel compound and organic light emitting device comprising the same Active CN112703189B (en)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
KR20180148563 2018-11-27
KR10-2018-0148563 2018-11-27
KR1020190153522A KR102341767B1 (en) 2018-11-27 2019-11-26 Novel compound and organic light emitting device comprising the same
KR10-2019-0153522 2019-11-26
PCT/KR2019/016488 WO2020111780A1 (en) 2018-11-27 2019-11-27 Novel compound and organic light emitting device comprising same

Publications (2)

Publication Number Publication Date
CN112703189A CN112703189A (en) 2021-04-23
CN112703189B true CN112703189B (en) 2023-10-31

Family

ID=71080723

Family Applications (8)

Application Number Title Priority Date Filing Date
CN201980063552.8A Active CN112771033B (en) 2018-11-27 2019-11-12 Novel compound and organic light emitting device comprising the same
CN201980060932.6A Active CN112739693B (en) 2018-11-27 2019-11-12 Novel compound and organic light emitting device comprising the same
CN201980063285.4A Active CN112789273B (en) 2018-11-27 2019-11-12 Compound and organic light emitting device comprising the same
CN201980059133.7A Active CN112673005B (en) 2018-11-27 2019-11-14 Novel compound and organic light emitting device comprising the same
CN201980059132.2A Active CN112673004B (en) 2018-11-27 2019-11-14 Novel compound and organic light emitting device comprising the same
CN201980060834.2A Pending CN112714763A (en) 2018-11-27 2019-11-15 Novel compound and organic light emitting device comprising the same
CN201980067110.0A Active CN112839939B (en) 2018-11-27 2019-11-22 Novel compound and organic light emitting device comprising the same
CN201980059738.6A Active CN112703189B (en) 2018-11-27 2019-11-27 Novel compound and organic light emitting device comprising the same

Family Applications Before (7)

Application Number Title Priority Date Filing Date
CN201980063552.8A Active CN112771033B (en) 2018-11-27 2019-11-12 Novel compound and organic light emitting device comprising the same
CN201980060932.6A Active CN112739693B (en) 2018-11-27 2019-11-12 Novel compound and organic light emitting device comprising the same
CN201980063285.4A Active CN112789273B (en) 2018-11-27 2019-11-12 Compound and organic light emitting device comprising the same
CN201980059133.7A Active CN112673005B (en) 2018-11-27 2019-11-14 Novel compound and organic light emitting device comprising the same
CN201980059132.2A Active CN112673004B (en) 2018-11-27 2019-11-14 Novel compound and organic light emitting device comprising the same
CN201980060834.2A Pending CN112714763A (en) 2018-11-27 2019-11-15 Novel compound and organic light emitting device comprising the same
CN201980067110.0A Active CN112839939B (en) 2018-11-27 2019-11-22 Novel compound and organic light emitting device comprising the same

Country Status (6)

Country Link
US (3) US20210355128A1 (en)
EP (2) EP3854792A4 (en)
JP (1) JP7088446B2 (en)
KR (8) KR102331904B1 (en)
CN (8) CN112771033B (en)
TW (2) TWI706948B (en)

Families Citing this family (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US12022730B2 (en) 2018-11-27 2024-06-25 Lg Chem, Ltd. Compound and organic light emitting device comprising the same
KR102331904B1 (en) 2018-11-27 2021-11-26 주식회사 엘지화학 Novel compound and organic light emitting device comprising the same
WO2020111602A1 (en) 2018-11-27 2020-06-04 주식회사 엘지화학 Novel compound and organic light-emitting element including same
CN112724125B (en) * 2019-10-28 2023-03-24 广州华睿光电材料有限公司 Nitrogen-containing organic compound and application thereof
TW202124389A (en) * 2019-12-27 2021-07-01 日商日鐵化學材料股份有限公司 Material for organic electroluminescence element, and organic electroluminescence element
JPWO2021131770A1 (en) * 2019-12-27 2021-07-01
CN117384166A (en) * 2021-06-18 2024-01-12 陕西莱特迈思光电材料有限公司 Nitrogen-containing compound, organic electroluminescent device and electronic device comprising same
WO2023277645A1 (en) * 2021-07-01 2023-01-05 Samsung Display Co., Ltd. Organic molecules for optoelectronic devices
CN115703759B (en) * 2021-08-10 2024-06-07 江苏三月科技股份有限公司 Compound containing triazine and pyrimidine groups and organic electroluminescent device containing same
US20230122972A1 (en) * 2021-09-08 2023-04-20 Samsung Sdi Co., Ltd. Compound for organic optoelectronic device, composition for organic optoelectronic device, organic optoelectronic device, and display device
CN113735793B (en) * 2021-09-24 2022-12-13 长春海谱润斯科技股份有限公司 Compound containing benzo five-membered heterocycle and organic electroluminescent device thereof
WO2023149635A1 (en) * 2022-02-02 2023-08-10 Samsung Display Co., Ltd. Organic molecules for optoelectronic devices
KR20240067826A (en) * 2022-11-09 2024-05-17 주식회사 엘지화학 Compound and organic light emitting device comprising the same
KR20240094080A (en) * 2022-11-23 2024-06-25 주식회사 엘지화학 Novel compound and organic light emitting device comprising the same
CN117756786A (en) * 2023-01-11 2024-03-26 陕西莱特光电材料股份有限公司 Organic compound, composition, organic electroluminescent device, and electronic device
CN117603192B (en) * 2023-01-11 2024-08-06 陕西莱特光电材料股份有限公司 Organic compound, composition, organic electroluminescent device, and electronic device
WO2024196207A1 (en) * 2023-03-17 2024-09-26 주식회사 엘지화학 Novel compound and organic light-emitting element comprising same
WO2024204430A1 (en) * 2023-03-27 2024-10-03 株式会社Kyulux Organic light emitting element

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20180047306A (en) * 2016-10-31 2018-05-10 성균관대학교산학협력단 Delayed fluorescence material and organic light emitting device having the delayed fluorescence material
CN112533900A (en) * 2018-10-26 2021-03-19 株式会社Lg化学 Deuterium-containing compound and organic light-emitting device comprising same

Family Cites Families (69)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5233631Y2 (en) 1971-04-22 1977-08-01
KR100430549B1 (en) 1999-01-27 2004-05-10 주식회사 엘지화학 New organomattalic complex molecule for the fabrication of organic light emitting diodes
DE10135513B4 (en) 2001-07-20 2005-02-24 Novaled Gmbh Light-emitting component with organic layers
CN100366703C (en) 2002-03-22 2008-02-06 出光兴产株式会社 Material for organic electroluminescent device and organic electroluminescent device using the same
KR101420608B1 (en) * 2004-12-24 2014-07-18 미쓰비시 가가꾸 가부시키가이샤 Organic compound, charge-transporting material, and organic electroluminescent element
DE102007024850A1 (en) * 2007-05-29 2008-12-04 Merck Patent Gmbh New materials for organic electroluminescent devices
JP5317470B2 (en) * 2007-12-27 2013-10-16 出光興産株式会社 Material for organic electroluminescence device and organic electroluminescence device using the same
JP5317471B2 (en) * 2007-12-27 2013-10-16 出光興産株式会社 Material for organic electroluminescence device and organic electroluminescence device using the same
JP5371312B2 (en) 2008-07-28 2013-12-18 ケミプロ化成株式会社 Novel dicarbazolylphenyl derivative, host material using the same, and organic electroluminescence device
US8759818B2 (en) 2009-02-27 2014-06-24 E I Du Pont De Nemours And Company Deuterated compounds for electronic applications
KR101801048B1 (en) * 2009-06-08 2017-11-28 에스에프씨 주식회사 Indolocarbazole derivatives and organoelectroluminescent device using the same
EP2461390B1 (en) * 2009-07-31 2018-05-23 UDC Ireland Limited Organic electroluminescent element
JP4474493B1 (en) * 2009-07-31 2010-06-02 富士フイルム株式会社 Organic electroluminescence device
JP4590020B1 (en) 2009-07-31 2010-12-01 富士フイルム株式会社 Charge transport material and organic electroluminescent device
EP2492987B1 (en) 2009-10-23 2018-01-24 Nippon Steel & Sumikin Chemical Co., Ltd. Organic electroluminescent device
JP4751955B1 (en) 2010-07-09 2011-08-17 富士フイルム株式会社 Organic electroluminescence device
JP4729642B1 (en) 2010-07-09 2011-07-20 富士フイルム株式会社 Organic electroluminescence device
KR101256205B1 (en) 2010-09-30 2013-04-19 (주)씨에스엘쏠라 Organic light emitting compound and organic light emitting device comprising the same
KR20130130757A (en) * 2010-11-24 2013-12-02 메르크 파텐트 게엠베하 Materials for organic electroluminescent devices
KR20120109744A (en) 2011-03-25 2012-10-09 롬엔드하스전자재료코리아유한회사 Novel compounds for organic electronic material and organic electroluminescence device using the same
KR101396171B1 (en) 2011-05-03 2014-05-27 롬엔드하스전자재료코리아유한회사 Novel organic electroluminescent compounds and an organic electroluminescent device using the same
KR20130020398A (en) 2011-08-19 2013-02-27 제일모직주식회사 Compound for organic optoelectronic device, organic light emitting diode including the same and display including the organic light emitting diode
KR101401639B1 (en) 2012-07-27 2014-06-02 (주)피엔에이치테크 Novel compound for organic electroluminescent device and organic electroluminescent device comprising the same
TWI599570B (en) 2012-09-28 2017-09-21 新日鐵住金化學股份有限公司 Compounds for organic electroluminescent devices and organic electroluminescent devices
JP6249150B2 (en) 2013-01-23 2017-12-20 株式会社Ｋｙｕｌｕｘ Luminescent material and organic light emitting device using the same
KR101627748B1 (en) * 2013-05-27 2016-06-07 제일모직 주식회사 COMPOUND, ORGANIC LiGHT EMITTING DIODE INCLUDING THE SAME AND DISPLAY INCLUDING THE ORGANIC LiGHT EMITTING DIODE
KR20150061174A (en) * 2013-11-26 2015-06-04 주식회사 두산 Organic compounds and organic electro luminescence device comprising the same
KR101773936B1 (en) * 2014-03-05 2017-09-01 주식회사 스킨앤스킨 New organic electroluminescent compounds and organic electroluminescent device comprising the same
US9773982B2 (en) * 2014-03-07 2017-09-26 Kyulux, Inc. Light-emitting material, organic light-emitting device, and compound
KR101754715B1 (en) 2014-04-08 2017-07-10 롬엔드하스전자재료코리아유한회사 Multi-component host material and organic electroluminescence device comprising the same
KR101729660B1 (en) * 2014-05-09 2017-04-26 (주)씨엠디엘 Novel compoung for organic electroluminescent device, organic electroluminescent device including the same and electric apparatus
US10461260B2 (en) 2014-06-03 2019-10-29 Universal Display Corporation Organic electroluminescent materials and devices
KR102273047B1 (en) 2014-06-30 2021-07-06 삼성디스플레이 주식회사 Organic light-emitting device
KR101820932B1 (en) * 2014-10-08 2018-01-22 주식회사 알파켐 New host material and organic electroluminescent device using the same
KR102154878B1 (en) * 2014-12-02 2020-09-10 두산솔루스 주식회사 Organic compounds and organic electro luminescence device comprising the same
US11758808B2 (en) 2015-03-27 2023-09-12 Samsung Display Co., Ltd. Ortho-substituted thermally activated delayed fluorescence material and organic light-emitting device comprising same
KR102388726B1 (en) 2015-04-29 2022-04-21 삼성디스플레이 주식회사 Organic light emitting device
US10403826B2 (en) 2015-05-07 2019-09-03 Universal Display Corporation Organic electroluminescent materials and devices
KR102146446B1 (en) * 2015-05-08 2020-08-20 코니카 미놀타 가부시키가이샤 π conjugated compounds, organic electroluminescent device materials, luminescent materials, luminescent thin films, organic electroluminescent devices, display devices and lighting devices
JP6813876B2 (en) 2015-10-27 2021-01-13 国立大学法人山形大学 Pyrimidine derivative, light emitting material made of it, and organic EL device using it
KR102430017B1 (en) 2015-10-28 2022-08-08 엘티소재주식회사 Hetero-cyclic compound and organic light emitting device using the same
KR20170060836A (en) * 2015-11-25 2017-06-02 에스케이케미칼주식회사 Compound for organic electroluminescent device and organic electroluminescent device comprising the same
KR102510282B1 (en) * 2015-12-24 2023-03-16 솔루스첨단소재 주식회사 Organic light-emitting compound and organic electroluminescent device using the same
CN105399696B (en) 2015-12-25 2019-12-24 上海天马有机发光显示技术有限公司 Organic electroluminescent compounds and organic photoelectric devices using the same
KR102577041B1 (en) 2015-12-30 2023-09-08 엘지디스플레이 주식회사 Organic compound, and Organic light emitting diode and Organic light emitting diode display device including the same
KR20170097820A (en) 2016-02-18 2017-08-29 삼성디스플레이 주식회사 Organic light emitting device
KR101956425B1 (en) 2016-03-25 2019-03-11 단국대학교 산학협력단 TADF Material and OLED Having the Same
KR101850245B1 (en) 2016-04-12 2018-04-19 주식회사 엘지화학 Compound and organic electronic device comprising the same
CN109071501B (en) 2016-05-04 2021-07-09 辛诺拉有限公司 Organic molecules, in particular for organic opto-electronic devices
DE102016112377B4 (en) 2016-07-06 2020-06-04 Cynora Gmbh Organic molecules, in particular for use in organic optoelectronic devices
CN107880028B (en) 2016-09-30 2021-03-02 中节能万润股份有限公司 Compound with aza-benzene as core and organic electroluminescent device
US10833276B2 (en) 2016-11-21 2020-11-10 Universal Display Corporation Organic electroluminescent materials and devices
KR20180063708A (en) 2016-12-02 2018-06-12 (주)피엔에이치테크 An electroluminescent compound and an electroluminescent device comprising the same
KR102055973B1 (en) 2016-12-07 2019-12-13 주식회사 엘지화학 Hetero-cyclic compound and organic light emitting device comprising the same
KR102533792B1 (en) 2016-12-09 2023-05-19 롬엔드하스전자재료코리아유한회사 Organic Electroluminescent Compound and Organic Electroluminescent Device Comprising the Same
KR20180092035A (en) * 2017-02-08 2018-08-17 주식회사 두산 Organic compound and organic electroluminescent device using the same
KR20180098809A (en) 2017-02-27 2018-09-05 삼성전자주식회사 Condensed cyclic compound and organic light emitting device comprising the same
JP6747642B2 (en) 2017-03-27 2020-08-26 エルジー・ケム・リミテッド Benzocarbazole compound and organic light emitting device containing the same
KR102366506B1 (en) 2017-04-06 2022-02-23 덕산네오룩스 주식회사 Compound for organic electronic element, organic electronic element using the same, and an electronic device thereof
WO2018237385A1 (en) * 2017-06-23 2018-12-27 Kyulux, Inc. Composition of matter for use in organic light-emitting diodes
CN114702480B (en) * 2017-07-14 2024-10-18 三星显示有限公司 Organic molecules, in particular for optoelectronic devices
WO2019076844A1 (en) 2017-10-18 2019-04-25 Cynora Gmbh Organic molecules, in particular for use in optoelectronic devices
EP3476915A1 (en) 2017-10-30 2019-05-01 Cynora Gmbh Organic molecules, in particular for use in optoelectronic devices
CN107954922A (en) 2017-11-28 2018-04-24 上海道亦化工科技有限公司 A kind of two carbazole derivates of xenyl and application thereof and organic electroluminescence device
CN107935914A (en) * 2017-11-28 2018-04-20 上海道亦化工科技有限公司 A kind of two carbazole benzene derivatives and application thereof and organic electroluminescence device
CN107987009A (en) * 2017-11-28 2018-05-04 上海道亦化工科技有限公司 A kind of carbazole derivates and application thereof and organic electroluminescence device
WO2019121112A1 (en) 2017-12-21 2019-06-27 Cynora Gmbh Organic molecules for use in optoelectronic devices
KR101926771B1 (en) * 2018-03-02 2018-12-07 주식회사 진웅산업 Organic light emitting diode comprising phosphorescence green host materials having thermally activated delayed fluorescence properties
KR102331904B1 (en) 2018-11-27 2021-11-26 주식회사 엘지화학 Novel compound and organic light emitting device comprising the same

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20180047306A (en) * 2016-10-31 2018-05-10 성균관대학교산학협력단 Delayed fluorescence material and organic light emitting device having the delayed fluorescence material
CN112533900A (en) * 2018-10-26 2021-03-19 株式会社Lg化学 Deuterium-containing compound and organic light-emitting device comprising same

Also Published As

Publication number Publication date
EP3842428A4 (en) 2021-11-03
KR102331904B1 (en) 2021-11-26
CN112739693A (en) 2021-04-30
KR20200063052A (en) 2020-06-04
US20210355128A1 (en) 2021-11-18
TW202026401A (en) 2020-07-16
CN112714763A (en) 2021-04-27
KR102352825B1 (en) 2022-01-18
CN112673005A (en) 2021-04-16
CN112771033A (en) 2021-05-07
JP7088446B2 (en) 2022-06-21
KR102341766B1 (en) 2021-12-22
US20210363132A1 (en) 2021-11-25
KR20200063053A (en) 2020-06-04
KR102341767B1 (en) 2021-12-22
CN112739693B (en) 2023-09-19
CN112673005B (en) 2023-10-10
EP3842428A1 (en) 2021-06-30
CN112771033B (en) 2024-01-23
TWI707943B (en) 2020-10-21
CN112789273B (en) 2023-12-29
US12037337B2 (en) 2024-07-16
US12098156B2 (en) 2024-09-24
CN112839939A (en) 2021-05-25
KR20200063048A (en) 2020-06-04
KR102265929B1 (en) 2021-06-16
EP3854792A4 (en) 2021-11-10
TWI706948B (en) 2020-10-11
KR20200063060A (en) 2020-06-04
CN112703189A (en) 2021-04-23
KR20200063049A (en) 2020-06-04
US20210399232A1 (en) 2021-12-23
KR102340254B1 (en) 2021-12-17
KR102341765B1 (en) 2021-12-22
JP2022500481A (en) 2022-01-04
TW202026291A (en) 2020-07-16
KR20200063050A (en) 2020-06-04
KR102311642B1 (en) 2021-10-12
KR20200063076A (en) 2020-06-04
CN112789273A (en) 2021-05-11
EP3854792A1 (en) 2021-07-28
CN112673004B (en) 2023-12-15
CN112839939B (en) 2024-01-19
KR20200063046A (en) 2020-06-04
CN112673004A (en) 2021-04-16

Similar Documents

Publication Publication Date Title
CN112703189B (en) Novel compound and organic light emitting device comprising the same
CN109661450B (en) Organic light emitting device
CN112055705B (en) Novel compound and organic light emitting device comprising the same
CN111094277B (en) Novel compound and organic light emitting device comprising the same
CN112041315B (en) Compound and organic light emitting device comprising the same
CN112424183B (en) Novel compound and organic light emitting device comprising the same
CN112888683B (en) Novel compound and organic light emitting device comprising the same
CN110520419B (en) Novel heterocyclic compound and organic light-emitting device comprising same
CN110753687B (en) Novel heterocyclic compound and organic light-emitting device comprising same
CN110573498B (en) Novel heterocyclic compound and organic light-emitting device comprising same
CN111655683B (en) Novel heterocyclic compound and organic light-emitting device comprising same
CN111989326B (en) Novel heterocyclic compound and organic light-emitting device comprising same
CN112204034A (en) Novel compound and organic light emitting device comprising the same
CN112533914A (en) Novel compound and organic light emitting device comprising the same
CN112449639B (en) Compound and organic light emitting device comprising the same
CN112119081B (en) Novel compound and organic light emitting device comprising the same
CN111971281B (en) Novel heterocyclic compound and organic light-emitting device comprising same
CN111902407B (en) Compound and organic light emitting device comprising the same
CN112135828B (en) Novel compound and organic light emitting device comprising the same
CN111630038B (en) Novel compound and organic light emitting device comprising the same
CN117616025A (en) Novel compound and organic light emitting device comprising the same
CN113260608B (en) Novel compound and organic light emitting device comprising the same
CN112739694B (en) Compound and organic light emitting device comprising the same
CN112424190B (en) Compound and organic light emitting device comprising the same
CN111868053B (en) Novel compound and organic light emitting device comprising the same

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant